Preparation and Characterization of High Performance MFI Zeolite Membrane in Ultradilute Solution

doi:10.15541/jim20170205

Abstract

Abstract:

High performance MFI-type zeolite membrane was successfully prepared in ultradilute solution (H₂O/SiO₂= 1000) on inexpensive and macroporous α-Al₂O₃ tubular support by secondary growth. Influences of seed size and H₂O/SiO₂ on morphology and pervaporation performance of the zeolite membranes were investigated. Results showed that the seed layer prepared with 0.4 μm seeds had higher crystal nucleus density which could increase the amount of the nucleation site on the support surface, resulting in a stronger induced effect on the growth of zeolite membrane. The low-concentration template and silicon source in ultradilute solution decreased the growth rate of zeolite crystals, which could reduce the zeolite membrane thickness and effectively inhibited the formation of intercrystalline defects. The flux and separation factor (α_{ethanol/water}) of the resulting MFI zeolite membrane achieved 4.09 kg/(m²·h¹) and 47, respectively, for separation of 5wt% ethanol/water mixture at 60℃. Ultradilute solution and low-cost macroporous α-Al₂O₃ tubular support reduced the preparation cost of MFI zeolite membranes and increased the flux, showing prospect of the potential industrial application of MFI-type zeolite membrane for removal of the low-concentration organic compounds in water.

Key words: MFI zeolite membrane, macroporous α-Al₂O₃ tubular support;, ultradilute solution, pervaporation

CLC Number:

TQ174

HUANG Pan, ZHOU Liang, LI Hua-Zheng, LI Hong-Jian, YANG Jian-hua, WANG Jin-Qu. Preparation and Characterization of High Performance MFI Zeolite Membrane in Ultradilute Solution[J]. Journal of Inorganic Materials, 2018, 33(3): 345-351.

Figures/Tables 11

Table 1 Preparation of Silicalite-1 seeds with different sizes

Sample	Precursor	Temp./℃	Average size/μm	Conc./wt%
A	1	96	0.4	0.35
B	2	100	0.8	0.35
C	2	150	1.3	2.5&0.35

Fig. 1 Surface and cross-sectional SEM images of the α-Al2O3 support(a)-(b), the support modified by large seeds(c, d) and the seed layers prepared with differently sized seeds (0.4 μm (e, f); 0.8 μm (g, h) and 1.3 μm (i, j))

Fig. 2 SEM images of MFI zeolite membranes prepared with different-size seeds in H2O/SiO2=1000 synthetic solution (a, b)-M1 0.4 μm; (c, d)-M2 0.8 μm; (e, f)-M3 1.3 μm

Table 2 Pervaporation performance of MFI zeolite membranes prepared with seeds of different size

No	Seed size/μm	H₂O/SiO₂	Time/h	J/(kg·m^-2·h^-1)	α
M1	0.4	1000	24	4.09	47
M2	0.8	1000	24	4.22	39
M3	1.3	1000	24	4.30	35
M4	0.4	1800	32	4.36	19
M5	0.8	1800	32	-	-
M6	1.3	1800	32	-	-

Fig. 3 SEM images of MFI zeolite membranes prepared with different-size seeds in H2O/SiO2=1800 synthetic solution (a, b)-M4 0.4 μm; (c, d)-M5 0.8 μm; (e, f)-M6 1.3 μm

Fig. 4 XRD patterns of MFI-type zeolite membranes prepared with H2O/SiO2 ratios of 200 (M7), 650 (M8), 1000 (M1), 1400 (M9). and 1800 (M4)

Fig. 5 SEM images of MFI-type membranes prepared with H2O/SiO2 ratios of 200 (a, b)-M7; 650 (c, d)-M8; 1400 (e, f)-M9

Table 3 Pervaporation performances of MFI-type zeolite membranes prepared from synthesis solutions with different H2O/SiO2

Sample	H₂O/SiO₂	Time /h	J/(kg·m^-2·h^-1)	α
M7	200	24	2.94	22
M8	650	24	3.60	32
M1	1000	24	4.09	47
M9	1400	24	4.40	43
M10	1800	24	4.90	11
M4	1800	32	4.36	19

Fig. 6 EDS analysis of MFI-type zeolite membranes prepared in synthetic solutions with different H2O/SiO2 ratios

Fig. 7 Pervaporation performance of MFI zeolite membrane prepared in synthetic solution with different H2O/SiO2 ratios for separation of 5wt% ethanol/water mixtures at 60℃

Table 4 Pervaporation performance of MFI membranes for ethanol/water mixtures

Membrane/Support	Pore size/μm	H₂O/SiO₂	Feed conc./wt%	Feed temp./℃	J/(kg·m^-2·h^-1)	α_{(ethanol/water)}	Ref.
Si-1/Ml-t	1.0	800	5	60	1.91	66	[22]
MFI/α-d	0.1+3.0	58	10	60	9.00	5	[14]
Si-1/α-t	2.0	120	5	60	1.81	89	[15]
Si-1/Ml-t	1.0	120	5	60	2.23	62	[15]
MFI/α-hf	0.1-0.2	165	3	60	2.90	66	[17]
MFI/α-t	1.0-3.0	165	5	60	1.36	85	[26]
MFI/α-t	3.0-4.0	1000	5	60	4.09	47	This work
MFI/α-t	3.0-4.0	1400	5	60	4.40	43	This work

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